Phenethyl bromide → 3-Hydroxy-4-(2-phenylethoxy)benzaldehyde

HRID 2213569Notes

Reaction equation

HRID 2213569 reaction equation
Br[CH2:2][CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[OH:10][C:11]1[CH:12]=[C:13]([CH:16]=[CH:17][C:18]=1[OH:19])[CH:14]=[O:15].C(=O)([O-])[O-].[Cs+].[Cs+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O>[OH:10][C:11]1[CH:12]=[C:13]([CH:16]=[CH:17][C:18]=1[O:19][CH2:2][CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[CH:14]=[O:15]

Participants

6

Reactant 3

HCID 7666Phenethyl bromideHCID 87683,4-DihydroxybenzaldehydeHCID 10796Cesium carbonate

Product 1

HCID 219574673-Hydroxy-4-(2-phenylethoxy)benzaldehyde

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolvent

Procedure

(2-Bromoethyl)benzene (20 mL, 0.14 mol, 2 eq) was added to a stirred solution of 3,4-dihydroxybenzaldehyde (10 g, 0.072 mol, 1 eq), tetra-n-butylammonium iodide (27 g, 0.072 mol, 1 eq) and cesium carbonate (14.2 g, 0.043 mol, 0.6 eq) in N,N-dimethylformamide (50 mL). The solution was stirred overnight, then concentrated in vacuo and diluted with ethyl acetate (200 mL). The organic solution was washed with 1M HCl (2×200 mL), and brine (200 mL), dried over sodium sulfate and evaporated. The residue was purified by chromatography on silica gel, eluting with toluene:ethyl acetate (19:1). This gave the product as a colourless oil which crystallized on standing (2.71 g, 15%). RF (toluene:ethyl acetate, 9:1) 0.31. 1H NMR (CDCl3) δ 9.84 (s, 1H, O═C—H), 6.96 (d, 1H, J 8.3 Hz, ArH), 5.64 (s, 1H, OH), 4.36 (t, 2H, J 7.2 Hz, OCH2CH2Ph), 3.17 (t, 2H, J 7.2 Hz, OCH2CH2Ph).

Workup

  1. concentrationconcentrated in vacuo
  2. additiondiluted with ethyl acetate (200 mL)
  3. washThe organic solution was washed with 1M HCl (2×200 mL), and brine (200 mL)
  4. dry with materialdried over sodium sulfate
  5. customevaporated
  6. customThe residue was purified by chromatography on silica gel
  7. washeluting with toluene:ethyl acetate (19:1)

Sources & evidence

ORD record
ord-a96c0ef87d6e46df906a55a33426f285
Source dataset
uspto-grants-2006_09
Patent number
US07105554B2

Reaction notes

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